JP2002512884A - Materials for introducing physiologically essential inorganic elements into drinking water - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention relates to the modification of organic ionites to impart to them specific properties, wherein the present invention relates to inorganic compounds of slightly lower solubility which enable the use of the modified ionites described above. It is involved in the regulation of drinking water and mainly in the addition of physiologically essential large and trace elements to said water. The use of this material makes it possible to introduce large and trace elements into the water and to remove organic and inorganic impurities from them, while stabilizing the separation of ions in the water. The use of this material allows a specific output (water flow rate) of up to 5 min- ¹ . The material of the present invention comprises essentially low solubility inorganic compounds and organic ionite, which, when fully dried, has a ratio of 35-90: 10-65 wt% ionite / low solubility compound. Has a porous structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates to the regulation of drinking water, and in particular to materials for introducing physiologically essential large and trace elements into drinking water. BACKGROUND ART Materials for regulating drinking water comprise rocks, including dolomite, which, in weight percent, are: calcium, 20; magnesium, 11; iron, 0.002;
Copper, 0.01; Cobelt, 0.001; Nickel, 0.002; Zinc, 0.01
It is known in the art to contain chromium, 0.002; vanadium, 0.001. As water passes through 1-5 mm granules of this mineral, ions of macroelements (calcium, magnesium) and trace elements (iron, copper, zinc), which are physiologically essential for human life, are introduced into drinking water. (Russian Patent No. 2,056,358,
IPCC02F 1/18, published on 96.03.20).

Such materials have the disadvantage that they cannot introduce other trace elements into them. The speed at which water passes through a material filled with such a material is not fast (1-2 L / h)
This is because physiologically essential elements are released only from the surface of the inorganic material. Compositions known in the art for fluoridating (regulating) drinking water include activated carbon and cellulose esters (preferably cellulose acetate) and fluorine ions (
Preferably, it comprises a material made of an inorganic compound containing calcium fluoride (which is hardly soluble). The particle size composition of the material is 0.3-1.5 mm. The component ratio in said material is from 5 to 83:17 to 95 in weight percent (Russian Patent No. 2092451, IPC C02F 1/68, 97.10.10.
Release). Such a material makes it possible to bring the water saturated with fluoride ions in an amount of 0.5 to 1.5 mg / l to a specific rate of water passing through said material of 0.5 to 5 min ^-1. To

[0003] The disadvantage of this material is that it is only used to introduce fluoride ions into drinking water. The less pronounced ion exchange properties of the granules of the composition material prevent its simultaneous use for the active removal of such harmful mixtures as heavy metals. Furthermore, the complexity of the method of producing this material is due in particular to the use of non-flammable liquid-acetone.

[0004] A material also known for introducing physiologically essential ions into deionized water consists of granules of activated carbon, on the surface of which pores there are poorly soluble inorganic compounds, which are The composition contains calcium and magnesium ions that are releasable in water. The deposition of said inorganic poorly soluble compounds in the pores of the activated carbon, by subjecting the activated carbon to a continuous treatment with a solution of a readily soluble substance, which enters the exchange reaction and results in the precipitation of one of the reaction products. Achieved. The activated carbon treated by each of the solutions must be dried at a temperature of 150-200 ° C. (Inventor's certificate No. 1608138 of the Soviet Socialist Republic, IPC CO2F
1/68, 90.11.23. Release).

[0005] Maintaining the calcium and magnesium ion concentrations of the filtered water at a physiologically required concentration of this known material is that the amount of water passed is 30 L and the input weight is 100 g. And when the flow rate is 50 ml / min. The specific rate of filtration is 0.5 min- ¹ . Due to its porous structure, the material adsorbs organic mixtures well enough, and it is also possible to retain heavy metal ions by physical adsorption. With the use of this material, there is also no penetrating effect during the interruption of the operation.

A major disadvantage of such a material is that it can only be used to introduce macromolecules such as magnesium, calcium, potassium. Other disadvantages of such materials are: the complexity of their preparation, the unproductive consumption of the reagents and the lack of chemisorption of heavy metal ions. The rate of filtration of water through such materials is not high.

[0007] The technical object of the present invention is therefore to ensure that deionized or drinking water is introduced with physiologically essential large and trace elements due to its stable release into said water. It is to provide simultaneous adsorption of a mixture of heavy metal ions and organic compounds from the wax material, said water, and an increase in the filtration rate of the water. DISCLOSURE OF THE INVENTION Materials for introducing physiologically essential additives into drinking or deionized water comprise organic ion exchangers, which have a porous structure in the air-dried state, as well as the And an inorganic hardly soluble compound on the surface thereof. The content of the hardly soluble compound in the material is 10 to 65 percent by weight.

[0008] Organic macropores or polymeric networks of strong and weak acidic cation exchangers with polystyrene, polyacryl and polymethacrylic matrices, and high and low basic anions with polystyrene and polyacrylic matrices Similar to the organic macropores or polymer networks of the exchangers, or their structure and properties, of pores with a total volume of 0.1-1.0 cm ³ / g and 0.3-1
. Other drugs with 5 mm granules are used as organic ion exchangers with a porous structure in the air-dried state.

As inorganic poorly soluble compounds (PSCs), said materials comprise inorganic salts, oxides, hydroxides, whose solubility is less than 8 g / l, and in their composition, Elements essential for the life of the animal, such as Ca, Mg, F, Se, Zn
, Cu, Fe, Mn, Cr and the like. P comprising physiologically essential elements
SC is formed as a result of exchange and redox reactions.

[0010] The method for producing the material comprises a continuous treatment of an organic ion exchanger with an inorganic ionic compound. Said ion exchanger is initially an inorganic compound having a solubility of at least 8 g / l, for example CaCl ₂ , MgSO ₄ , NaF, Na ₂ SeO ₃
, ZnSO ₄ , CuSO ₄ , FeSO ₄ , MnSO ₄ , KMnO ₄ , Cr ₂ (S
O ₄ ) ₃ , Na ₂ SnO ₃ , HCl, NaOH, KOH, K ₂ CO ₃ , HClO
And one of the ions of the compound passes through the ion exchanger as a counterion. Next, the ion exchanger is a second ion exchanger having a solubility of 8 g / l or more.
One of the ions reacts with the counter-ion of the ion exchanger and has a solubility of less than 8 g / l in the pores and on the surface of the ion exchanger (difficult to form). (Soluble compounds). The above compounds can be used as the second inorganic compounds mentioned above. In some cases, to achieve the regularity of release of ions into water and the required concentration, these operations are
Repeated five times, the PSC content in the material reaches 10-65% by weight. Exemplary Embodiment 1 of the Present Invention

[0011] The anion exchanger AV-17-10P is treated with Na ₂ SO ₄ solution until their conversion to the sulfate form is 70-100%. Next, the anion exchanger was prepared using a 5% solution of CaCl ₂ under static conditions and a solid to liquid (s
/ L) ratio = 1: 2. After 3 hours of contact, the solution is decanted and the anion exchanger is washed with distilled water. The above operation is repeated twice. The material contains a poorly soluble compound (PSC) CaSO ₄ in its pores at 6% by weight.
Contains 5%. The PSC content of the material is determined from the difference in the concentration of calcium ions in the starting solution and the equilibration solution.

In an amount of 10 cm ^3, the resulting material was placed in a column having an internal diameter of 11 mm and low deionized water was added to the material (total hardness (TH) of 0.5
mg eq / l). The content of calcium ions in the water is 1,10,
After the passage of 20 and 30 liters of water, it is determined at the outlet of the column. When passing through water, the specific output is 3.0 min- ¹ . After the passage of 10 and 20 liters of water, a sample is taken, the flow is stopped for 24 hours and after this interval the sample is taken again. The content of calcium ions is determined at the outlet of the column. Table 1 shows the components of the material and the parameters of the method for producing the material. Table 2 shows the analysis of the ion content in water and the physiological norm. Example 2

The cation exchanger KU-23 is treated with a CaCl ₂ solution until its conversion to the calcium form is 80-100%. Next, the anion exchanger was changed to N
Treated with a 3% solution of aF under static conditions, s / l ratio = 1: 3. After 2 hours of contact, the solution is decanted and the anion exchanger is washed with distilled water. Said material contains PSC CaF ₂ in an amount of 16% by weight. PSC in the material
The content is determined from the difference in the fluoride ion concentration of the starting and equilibrating solutions. The following procedure is as described in Example 1 in which the material is collected in an amount of 3 cm ³ and 3
Except that deionized water with TH of mg eq / l passed through the column and the content of fluoride ion was determined from the filtrate. Example 3

The cation exchanger S-106 (PUROLITE) is treated with CuSO ₄ until its conversion to copper form is 60-90%. Next, the cation exchanger is N
It is treated with a 10% solution of aOH, under dynamic conditions in the column, by consuming three times the volume of reagent per volume of the cation exchanger. After the contact, the cation exchanger is washed with distilled water. Repeat the above operation three times. The material comprises PSC Cu (OH) ₂ in an amount of 58% by weight. For the determination of the PSC content in the material, the precipitate is dissolved and the content of copper (II) ions therein is determined. The next procedure is similar to Example 1, except that deionized water with 3 mg eq / l of TH passes through the column and the content of copper ions is determined in the filtrate. Example 4

The anion exchanger A-835 (PUROLITE) is treated with Na ₂ SeO ₃ solution until its conversion to the selenite form is complete. Next, the above anion exchanger was treated with a 2% solution of AgNO ₃ under static conditions under an s / l ratio of 1: 1.
Process with 0. After 6 hours of contact, the solution is decanted and the material is washed with distilled water. Said material comprises PSC AgSeO _{3 in} an amount of 10% by weight. To determine the PSC content in the material, the precipitate was dissolved and the content of silver and selenite ions therein was determined spectrophotometrically using 3,3'-diaminobenzidine as a reagent. decide. The next procedure is similar to Example 1, except that the content of selenite ions is determined in the filtrate. Example 5

This example is similar to Example 1, except that the anion exchanger is first converted to the hydroxyl form and then treated with a 3% solution of MgSO ₄ . Said material comprises PSC Mg (OH) ₂ in an amount of 43% by weight. To determine the PSC content in the material, the precipitate is dissolved and the content of magnesium ions is determined. The following procedure is the same as in Example 1, except that the content of magnesium ions is determined in the filtrate. Example 6

The cation exchanger S-150 (PUROLITE) is treated with a solution of ZnSO ₄ until its conversion to the zinc form is 80-100%. Then the cation exchanger, with a 5% solution of Na ₂ CO _3, under dynamic conditions, is processed by the consumption of the solution volume of 3 times per volume of the cation exchanger. Thereafter, the cation exchanger is treated with distilled water. The above operation is repeated twice. Said material comprises PSC ZnCO _{3 in} an amount of 61% by weight. To determine the PSC content in the material, dissolve the precipitate and determine the zinc ion content in the solution. The next procedure is the same as in Example 1, except that 5 cm ³ of the material is placed on the column and the content of zinc ions is determined in the filtrate. Example 7

The anion exchanger AN-511 is treated with NaOH solution until its conversion to the hydroxyl form is complete. The cation exchanger is then treated with a 5% solution of KMnO ₄ under static conditions with an s / l ratio of 1: 2. After 0.5 hours of contact, the solution is decanted and the material is washed with distilled water. The material in accordance with conversion to manganese, including PSC Mn (OH) ₂ and MnO ₂ in an amount of 25% per weight. To determine the PSC content in the material, the material is ashed and the manganese content is determined in the residue. Example 8

This example is similar to Example 1 in which the cation exchanger KU-23 is used as a carrier for the PSC, said cation exchanger converts to the calcium form, and Na ₂
Except for treating with a 1% solution of SO ₄ at a s / l ratio of 1:20. The total number of processes is one. The material contains PSC CaSO ₄ in an amount of 10% by weight. Example 9

The cation exchanger KU-23 is treated with a solution of CaCl ₂ until its conversion to the calcium form is 80-100%. Next, the cation exchanger is
Treatment with a 30% solution of MgSO ₄ under static conditions at an s / l ratio = 1: 1.
After 2 hours of contact, the solution is decanted and the cation exchanger is treated with a 5% solution of Na ₂ CO ₃ under static conditions at an s / l ratio of 1: 3. After one hour of contact, the solution is decanted and the cation exchanger is washed with distilled water. The PSC CaSO ₄ and MgCO ₃ content in the material is 45% by weight. The PSC content in the material is determined from the difference in calcium and magnesium ion concentrations in the starting and equilibrating solutions. The following procedure is similar to that used in Example 1 in which deionized water with 0.05 mg eq / l of TH passed through the column and the content of calcium and magnesium ions in the filtrate Except to be determined. Example 10

This example is similar to Example 1, except that the cation exchanger KU-23 is responsible for the PSC.
The cation converter is converted to the calcium form and _Two SO_Four With the s / l ratio = 1: 2 using a 5% solution of processing
Is 6. The material is PSC CaSO_Four 72% by weight
Include in quantity.

The use of a material comprising an organic ion exchanger in an amount of 35-90% by weight and having a porous structure in the air-dried state allows the constant release of physiologically essential ions into water, It is provided at a specific rate of water passing through the material of 0.5 min- ¹ or more. If the content of the poorly soluble inorganic compound on the anion exchanger is less than 10% by weight, not enough physiologically essential ions have penetrated the water. If the PSC content on the ion exchanger is greater than 65% by weight, the required number of treatments will increase exponentially, thereby complicating the process for producing the material and the stability of the operation of the material. descend.

As can be seen from the examples and tables described, the organic ion exchanger having a certain structure and having a poorly soluble inorganic compound in a certain ratio thereof is used as the material to be used as the carrier. The use of water allows the introduction of trace elements as well as macroelements into water, increasing the rate of water filtration, which is almost impossible to achieve with known technical solutions. there were. By the use of such materials, the specific output (water passage speed) can be increased by a factor of six.

The number and type of organic ion exchangers and poorly soluble compounds applied are not limited to the examples described.

[0025]

[Table 1]

[0026]

[Table 2]

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AU, BG, BR, CA, CZ, EE, HU, IL, IN, JP, KR, LT, LV, MX , NO, PL, SI, SK, TR, UA, US, UZ, YU (72) Inventors Krasnov, Mikhail Stanisvovic Russia, Mosko, 111020, Strozebaya Ulica, D. 18, Kbarczira 23 (72) Inventors Amiralagov, Mikhail Sergeevich, Moscow, 123309, Ulica demiyama Bednogo, D. 24, Car. 4, Kubarczira 64 (72) Inventors Bobe, Leonid Sergeevich, Moscow, Russia, 125252, Ulica Georgiyu Deja, Day. 3 Kubaruchira 75

Claims (1)

[Claims] 1. A material for introducing a physiologically essential inorganic element into water, said material comprising a porous carrier, which comprises an inorganic hardly soluble compound in its pores, and is air-dried. An organic ion exchanger having a porous structure in the state is used as the carrier, and the ratio of the ion exchanger to the hardly soluble compound is 35-90: 10-65% by weight. Material to do.